Fluid catalytic cracking process

ABSTRACT

A hydrocarbon feed is cracked in the presence of a fluid zeolite catalyst or a catalyst of comparable activity and/or selectivity which produces a transient maximum gasoline yield at a residence time of 5 seconds or less and in the presence of a diluent vapor or vapors which lower the partial pressure of the hydrocarbon feed and increase gasoline selectivity. Residence time is established by controlling the total charge rate of hydrocarbon and diluent vapor. The ratio of diluent vapor or vapors to hydrocarbon feed is also controlled so that a greater yield of gasoline is recovered from the process than could be recovered in the absence of the diluent vapor.

United States Patent 72] Inventor Millard C. Bryson Conway, Pa. James R. Murphy Huntington Station, NY.

[21] Appl. No. 836,383

[22] Filed June 25, 1969 [45] Patented Nov. 2, 1971 [73] Assignees Gulf Research 8; Development Company Pittsburgh, Pa.

[54] FLUID CATALYTIC CRACKING PROCESS 10 Claims, 3 Drawing Figs.

[56] References Cited UNITED STATES PATENTS 3,246,960 4/1966 Sharp et a1 23/288 Primary Examiner-Delbert E. Gantz Assistant Examiner-G. E. Schmitkons Attorneys-Meyer Neischloss, Deane E. Keith and Alvin E.

Ring

ABSTRACT: A hydrocarbon feed is cracked in the presence of a fluid zeolite catalyst or a catalyst of comparable activity and/or selectivity which produces a transient maximum gasoline yield at a residence time of 5 seconds or less and in the presence of a diluent vapor or vapors which lower the partial pressure of the hydrocarbon feed and increase gasoline selectivity. Residence time is established by controlling the total charge rate of hydrocarbon and diluent vapor. The ratio of diluent vapor or vapors to hydrocarbon feed is also controlled so that a greater yield of gasoline is recovered from the process than could be recovered in the absence of the diluent vapor.

CONVERSION: PER 6511/7 BY VOLUME 0 FRESH FEED EFFECT OF MDROCARBO/V PdfiT/AL PRESSURE 6 5/6) 47 MlQ/OUS (O/V7716 7' TIMES (SECONQS) PATENTEUuuv 2 197:

SHEET 1 [IF 3 a 70.5 SECONDS INVENTORS. M/LLARD C. BRKSO/V JAMES MURPHY PATENTEU 2 SHEET 3 UP 3 INVENTORS. M/LLARD C. BRYSO/V JAMES R. MURP/rl FLUID CATALYTIC CRACKING PROCESS This invention relates to the cracking of a petroleum hydrocarbon feed stock to gasoline in the presence of a highly active fluid cracking catalyst such as a crystalline aluminosilicate zeolite or a catalyst of comparable activity, or selectivity, or both.

Natural or synthetic zeolite aluminosilicate cracking catalysts exhibit high activity in the cracking of hydrocarbon oils both in terms of total conversion of feed stock and in terms of selectivity towards gasoline production. The present invention relates to a method for improving the selectivity to gasoline production in cracking processes utilizing a fluidized zeolitic cracking catalyst or a catalyst of comparable activity and/or selectivity.

In fluid catalytic cracking operations it is generally advantageous to operate the cracking reactor at pressures in the range of about 20 to 30 pounds per square inch gauge and it is undesirable in terms of the integrated operation including catalyst regeneration and power recovery from regenerator flue gases for reactor pressures to fall significantly below this level. For example, catalyst regeneration is generally favorably influenced by elevated temperatures and pressures. Furthermore, in systems where regenerator flue gas is utilized to drive a turbine to compress combustion air to be supplied to the regenerator, it is important to maintain an elevated pressure in the regenerator in order to obtain efficient turbine operation. Since spent catalyst must flow from the reactor zone to the regenerator, a correspondingly high pressure is consequently required in the reactor in order to urge catalyst towards the regenerator. However, as shown below, relatively high reactor hydrocarbon feed pressures are less favorable to gasoline selectivity in the cracking operation than relatively low pressures.

in accordance with the present invention a method is presented for advantageously improvingoperation of a reaction process employing a zeolitic or similar fluidized cracking catalyst without lowering the pressure in the reaction zone or catalyst disengaging or stripping vessel. We have discovered that an unexpected advantage occurs by charging a diluent gas to the inlet of the cracking reaction zone to lower the partial pressure of the charge hydrocarbon in the reaction zone without disturbing the total pressure in the system. Any diluent which is a vapor or becomes a vapor under the conditions of the reaction zone can be used. An inert gas such as steam or nitrogen is a suitable diluent. A mixture of gases can be employed. If the diluent is a hydrocarbon, it should desirably have a boiling point below about 430 F., i.e., it should be a gasoline range hydrocarbon or lighter. If it boils above the gasoline range it will itself be a portion of the cracking feed. Recycle methane or ethylene could be employed. We have found that a lower hydrocarbon feed partial pressure at any given reaction zone total pressure produces the unexpected effect of increasing the selectivity to gasoline production at a given conversion level of fresh feed or, conversely, requiring a lower conversion of total feed to produce a given gasoline yield.

Although it has been known that the use of an inert diluent such as steam at the hydrocarbon feed zone accomplishes certain advantageous effects in a fluid catalytic cracking opera tion such as assisting in fluidization of catalyst, vaporization of liquid feed, dispersal of catalyst into hydrocarbon feed, increasing reaction rate, etc., the improvement in gasoline selectivity has not heretofore been appreciated. We have further discovered that the gasoline selectivity advantage is transient and is lost if the cracking process is not terminated in a timely manner, as explained below. Because of its transient nature the selectivity advantage has heretofore been effectively masked.

it has previously been considered that the amount of steam to be employed in a fluid catalytic cracking process should not be great in order to avoid a reduction in residence time, and thereby a loss in conversion. However, in accordance with the present invention the amount of steam or other inert gas must be sufficient to produce a significant reduction in partial pressure of the incoming hydrocarbon capable of being cracked to gasoline. Although the initial increments of partial pressure reduction exert a greater effect upon gasoline selectivity than later increments, the greater the amount of steam or other inert gas introduced relative to hydrocarbon feed the greater will be the effect upon selectivity. For example, 10 mol percent steam based on hydrocarbon charge will reduce the partial pressure of the hydrocarbon charge 10 percent, 15 mol percent steam will reduce the partial pressure of the hydrocarbon charge 15 percent, etc., and the greater the reduction in partial pressure the greater the gasoline selectivity advantage it is possible to achieve in accordance with this invention.

in accordance with the present invention it has further been discovered that the selectivity advantage due to the presence of an inert gas, which is not itself capable of being cracked to gasoline, is most significant in the very early stages of the cracking reaction, which is also the period in which most of the cracking of fresh feed occurs. In fact, the curve of production of cracked hydrocarbon vapors from fresh feed with time is exponential with the greatest rate of cracking occurring at the outset of the reaction so that the cracked vapors themselves quickly reduce the partial pressure of the unreacted feed. However, by the time these vapors are produced most of the cracking has been completed. The extent of cracking of fresh hydrocarbon feed with a zeolite catalyst is considerably greater in the first 0.1 second interval in the reaction zone than in the second 0.1 second interval. Similarly, the extent of cracking of fresh hydrocarbon charge is considerably greater in the first 0.2 second interval in the reaction zone than in the second 0.2 second interval. For example, after the hydrocarbon feed has been in the reaction zone for about 0.1 second it is about 40 percent converted and afier about 1.0 second conversion increases only to about 70 to percent.

in control methods for fluid catalytic cracking operations according to the prior art, a vapor such as steam was added to the inlet of an elongated riser or reaction zone to assist dispersal of catalyst into hydrocarbon. The amount of steam was not considered particularly critical. Reactor residence time (space velocity) was then adjusted to control gasoline yield in the reactor effluent. If analysis of reactor effluent indicated an adjustment of the residence time was required, the hydrocarbon flow rate was adjusted. But no criticality was attached to the fact that this adjustment varied the ratio of steam to hydrocarbon at the reaction zone inlet. In accordance with the present invention reaction zone residence time is established not only by establishing the total charge rate including both hydrocarbon and steam but also by establishing the ratio of steam to hydrocarbon in the charge in the manner described below. We have now discovered and it is shown below that control of the ratio of steam to hydrocarbon in the charge and control of the total charge rate including both steam and hydrocarbon are interdependent and interdependently exert a critical effect on gasoline yield.

Although zeolitic aluminosilicates are especially useful catalysts for purposes of the present invention, any silica alumina or other cracking catalyst which is sufficiently active and/or selective to be capable of producing a transient maximum or peak gasoline yield from the total fresh hydrocarbon feed capable of being cracked to gasoline at residence times of 5 seconds or less are within the purview of this invention. The maximum gasoline yield obtained at residence times within 5 seconds is transient and rapidly diminishes. After a residence time of 1 second, most of the fresh hydrocarbon feed is converted and there is a sharp drop in rate of conversion of fresh feed. However, if the hydrocarbon continues to remain in contact with the catalyst, products of the earlier cracking operation themselves in turn undergo cracking. This occurrence is termed aftercracking." Since there is a greater abundance of cracked material than uncracked material after only about %to 1 second of reaction zone residence time or less the situation rapidly arises wherein considerably more cracking of cracked than uncracked material can occur. When this situation prevails, the desired gasoline product initially produced at a high selectivity in accordance with the present invention becomes depleted dueto aftercracking at a faster rate than it is replenished due to cracking of remaining uncracked feed so that the selectivity advantage initially achieved is subsequently lost at a significant rate. If timely disengagement of hydrocarbon and catalyst does not occur prior to the occurrence of a significant amount of aftercracking the very existence of the earlier advantageous selectivity effect can be entirely masked. This invention requires substantially instantaneous disengagement of catalyst and hydrocarbon as these materials exit from the reaction zone into a disengaging vessel.

In accordance with the present invention a preheated liquid hydrocarbon charge and a fluid zeolite or comparable cracking catalyst is added to a cracking reaction zone together with an inert gaseous diluent such as steam, nitrogen, recycle methane or ethylene, etc. The liquid hydrocarbon charge is substantially instantaneously vaporized and the quantity of inert diluent is sufficient to accomplish a substantial reduction in the partial pressure of the hydrocarbon charge. The selectivity to gasoline production is enhanced due to the lower hydrocarbon partial pressure at the onset of cracking of the fresh feed due to the presence of the diluent. In order not to subsequently lose the selectivity advantage the hydrocarbon is permitted to remain in the presence of the catalyst only as long as further conversion of uncracked hydrocarbon produces a significant increase in gasoline yield. The system is controlled so that substantially at the time when further conversion of uncracked hydrocarbon produces no significant net increase in gasoline yield or at the time when some decrease in gasoline yield ensues the catalyst and hydrocarbon are substantially instantaneously disengaged from each other to prevent aftercracking of gasoline product from destroying the selectivity advantage initially achieved due to the diluent partial pressure effect. Analysis of the product to measure total conversion of fresh feed or gasoline yield or both will aid in controlling the reactor in accordance with this invention. These analyses will provide a measure of gasoline selectivity for controlling the reactor. Reaction time duration can be adjusted by regulation of total feed rate, including hydrocarbon and steam, where the reactor height is fixed.

In accordance with this invention, the reactor is operated so that there is a continual increase in gasoline throughout substantially the entire length of the reactor coupled with a decrease in fresh feed, which means that the reaction is terminated at or near the time of maximum gasoline yield. There is a substantial absence of backmixing in the reactor since this would be conducive to aftercracking. Backmixing can be caused by an excessive linear velocity which gives rise to turbulence or by the formation of a dense catalyst bed which induces turbulence in flowing vapors. The hydrocarbon remains in the reactor only until a decrease in fresh feed content is not accompanied by any substantial further net increase in gasoline. Maximum gasoline yield is accompanied by maximum gasoline selectivity.

The overall time of contact between hydrocarbon and catalyst can be as low as about 0.5 second or less but not greater than about 5 seconds and will depend upon many variables in a particular process such as the boiling range of the charge, the particular catalyst, the amount of carbon on the regenerated catalyst, the catalyst activity, the reaction zone temperature, the polynuclear aromatic content of the hydrocarbon feed, etc. Some of these variables can affect one another. For example, if the fresh hydrocarbon charge includes a considerable quantity of polynuclear aromatics, the reaction should be permitted to proceed long enough to crack any monoor di-aromatics or naphthenes because these compounds produce relatively high gasoline yields and are the most readily crackable aromatics but the reaction should be terminated before significant cracking of other polynuclear aromatics occurs because cracking of these latter compounds occurs at a slower rate and results in excessive deposition of carbon on the catalyst. It is clear, that no fixed cracking time duration can be set forth but the time will have to be chosen within the range of this invention depending upon the particular system. In one system, slightly exceeding a 1.0 second residence time might result in such severe aftercracking that the selectivity advantage would be lost while in another system unless a 1.0 second residence time is appreciably exceeded there might not be sufficient cracking of charge hydrocarbon to render the process economic. Generally, the residence time will not exceed 2.5 or 3 seconds and 4 second residence times will be rare.

. Reference to FIG. 1 will illustrate the significance of the present invention. FIG. 1 contains curves semiquantitatively relating the amount of unreacted charge and gasoline, as percent based on fresh feed, to reaction zone residence time. The curve of unreacted charge which is typical of most fluid cracking charge stocks shows that the amount of unreacted charge asymptoticallyv approaches a value somewhat less than 20 percent of fresh feed within residence times of this invention. The curves showing quantity of gasoline produced show that the quantity of gasoline produced rapidly reaches a somewhat flat maximum or peak which generally coincides with the time at which the cracking of unreacted charge is substantially diminished. The gasoline yield at the peak for a given feed will be determined mostly by reactor temperature, to an extent by the level of carbon on the catalyst and to an extent by the catalyst to oil ratio. After reaching a peak. the gasoline level diminishes because the aftercracking of gasoline predominates over production of gasoline from the unreacted feed. The lower of the two gasoline curves shown in FIG. I indicates the level of gasoline in the reaction zone assuming substantially no inert diluent such as steam is introduced to the inlet zone of the reactor. The upper of the two gasoline curves schematically shows the higher gasoline level achieved by adding an inert diluent such as steam to the inlet of the reaction zone which lowers the hydrocarbon feed partial pressure and thereby increases selectivity to gasoline.

Assuming a fluid cracking process is operating with steam addition and the gasoline yield is at point A shown in FIG. I where significant aftercracking has occurred. In order to reduce the extent of aftercracking it is decided to increase the charge rate of hydrocarbon into the reaction zone, thereby reducing hydrocarbon residence time. Residence time is usually adjusted by adjustment of hydrocarbon charge rate rather than steam charge rate since for any given percentage increase or decrease in charge rate of steam or hydrocarbon, the effect upon reaction residence time will be much greater in the case of the hydrocarbon adjustment because the total amount of hydrocarbon charged is so much greater than the total amount of steam charged. Due to the shorter residence time and concomitant reduction in aftercracking a higher gasoline yield B is achieved. However, because the hydrocarbon partial pressure at the reaction zone inlet has been increased by an increase in hydrocarbon flow rate, the point B is removed from the upper gasoline curve in the direction of the lower gasoline curve and is outside the crosshatched zone which denotes the range of this invention. The crosshatched zone shown in FIG. 1 denotes the transient elevated gasoline yields of this invention which can be recovered by the use of an inert vapor but which could not be recovered absent an inert vapor. On the other hand, if the same decrease in hydrocarbon residence time were achieved by increasing both hydrocarbon and steam flow rate in the same ratio so that the partial pressure of hydrocarbon at the reaction zone inlet remained unchanged at the new residence time, the new operating point would be at B, instead of B, which is within the range of the present invention. (Of course, if the same total flow rate were achieved by increasing the ratio of steam to hydrocarbon the new operating point would be above B and the area covered by the crosshatched zone of this invention would be enlarged.) Now, if the hydrocarbon charge rate is again increased to further reduce residence time, the point C is reached which is further removed from the upper gasoline curve in the direction of the lower gasoline curve than is point B because the hydrocarbon partial pressure is further increased in going from point B to point C. Again, because of the increase in hydrocarbon partial pressure, point C is outside the range of the invention. On the other hand, if the same residence time indicated at point C is achieved by increasing the flow rate of both steam and hydrocarbon, rather than hydrocarbon alone, so that the hydrocarbon partial pressure at the new residence time is the same as it was at point A, the point C is achieved which is within the range of this invention.

it is seen from FIG. 1, that operating points B and C represent essentially similar gasoline conversion levels occurring at different residence times apparently indicating that these points lie close to a flat maximum gasoline yield. However, points 8 and C lie outside the range of the present invention while operating points B and C, which are within the range of this invention, lie at higher gasoline yield levels than points B and C, even through points B and B and points C and C represent the same residence times, respectively. Starting from point A, point B is reached by the method of lowering residence time via a change in both steam flow rate and hydrocarbon flow rate while, also starting from point A, point B is reached by the method of changing hydrocarbon flow rate only to achieve the same residence time as point B. Starting from point B, pointC' is reached by changing both steam flow rate and hydrocarbon flow range to lower the residence time, while point C is reached by the simpler method of changing hydrocarbon flow rate only to achieve the same residence time as at point C. It is apparent that to achieve the gasoline selectivity advantage of the present invention, the residence time and the apportioning of steam and hydrocarbon flow rates to achieve said residence time are interdependent and represent a critical combination for purposes of process control.

In any particular process the gasoline yield and residence time values which encompass the gasoline selectivity advantage of the present invention will depend upon many variables peculiar to the particular process. These variables include the particular catalyst which is employed, the level of carbon on the regenerated catalyst, catalyst activity and/or selectivity, the temperature, the refractory characteristics of the feed, etc. The extent of the selectivity advantage of this invention might be as low as '6 percent to 1 percent or as high as 3 to 5 percent depending upon the ratio of diluent vapor to hydrocarbon feed at the reactor inlet. Where gasoline is the most economically desirable product of the cracking operation, the

economic value of a selectivity advantage of even $9 or 1 percent actually recovered as effluent is considerable in a commercial reactor unit which processes 100,000 or 150,000 barrels per day of hydrocarbon feed.

The reaction temperature in accordance with this invention is at least about 900 F. The upper limit can be about 1,100 F., or more. The preferred temperature range is 950 to 1,050 F. The reaction total pressure can vary widely and can be, for example, 5 to 50 p.s.i.g., or preferably, to 30 p.s.i.g. The maximum residence time is 5 seconds, and for most charge stocks the residence time will be about 1.5 or 2.5 seconds or, less commonly, 3 or 4 seconds. For high molecular weight charge stocks which are rich in aromatics a 0.5 to 1.5 second residence time could be suitable in order to crack monoand di-aromatics and naphthenes which are the aromatics which crack most easily and which produce the highest gasoline yield, but to terminate the operation before appreciable cracking of polyaromatics occurs because these materials produce high yields of coke and C, and lighter gases. The length to diameter ratio of the reactor can vary widely, but the reactor should be elongated to provide a high linear velocity, such as to 75 feet per second, and to this end a length to diameter ratio above 20 or 25 is suitable. The reactor can have a uniform diameter or can be provided with a continuous taper or a stepwise increase in diameter along the reaction path to maintain a nearly constant velocity along the flow path. The amount of diluent can vary depending upon the ratio of hydrocarbon to diluent desired for control purposes. If

steam is the diluent employed, a typical amount to be charged can be about 10 percent by volume, which is about 1 percent by weight, based on hydrocarbon charge. A suitable but nonlimiting proportion of diluent gas, such as steam or nitrogen, to fresh hydrocarbon feed can be 0.5 to 10 percent by weight.

A zeolite catalyst is a highly suitable catalytic material in accordance with this invention. A mixture of natural and synthetic zeolites can be employed. Also a mixture of crystalline zeolitic organosilicates with nonzeolitic amorphous silica aluminas is suitable as a catalytic entity. Any catalyst containing zeolitic material or otherwise which provides a transient maximum gasoline yield within a 5 second residence time is suitable. The catalyst particle size must render it capable of fluidization as a disperse phase in the reactor. Typical and nonlimiting fluid catalyst particle size characteristics are as follows:

These particle sizes are usual and are not peculiar to this invention. A suitable weight ratio of catalyst to total oil charge is about 4:1 to about 1221 or 15:] or even 25:1, generally, or 6:1 to 10:1, preferably. The fresh hydrocarbon feed is generally preheated to a temperature of about 600 to 700 F. but is generally not vaporized during preheat, and the additional heat required to achieve the desired reactor temperature is imparted by hot, regenerated catalyst.

The weight ratio of catalyst to hydrocarbon in the feed is varied to affect variations in reactor temperature. Furthermore, the higher the temperature of the regenerated catalyst the less catalyst is required to achieve a given reaction temperature. Therefore, a high regenerated catalyst temperature will permit the very low reactor density level set forth below and thereby help to avoid backmixing in the reactor. Generally, catalyst regeneration can occur at an elevated temperature of about 1,240 F. or l,250 F. or more to reduce the level of carbon on the regenerated catalyst from about 0.6 to 1.5 to about 0.05 to 0.3 percent by weight. At usual catalyst to oil ratios in the feed, the quantity of catalyst is more than ample to achieve the desired catalytic effect and therefore if the temperature of the catalyst is high, the ratio can be safely decreased without impairing conversion. Since zeolitic catalysts are particularly sensitive to the carbon level on the catalyst, regeneration advantageously occurs at elevated temperatures in order to lower the carbon level on the catalyst to the stated range or lower. Moreover, since a prime function of the catalyst is to contribute heat to the reactor, for any given desired reactor temperature the higher the temperature of the catalyst charge the less catalyst is required. The lower the catalyst charge rate the lower the density of the material in the reactor. As stated, low reactor densities help to avoid backmixing.

The reactor linear velocity, while not being so high that it induces turbulence and excessive backmixing, must be sufficiently high that substantially no catalyst accumulation or buildup occurs in the reactor because such accumulation itself leads to backmixing. (Therefore, the catalyst to oil weight ratio at any position throughout the reactor is about the same as the catalyst to oil weight ratio in the charge.) Stated another way, catalyst and hydrocarbon at any linear position along the reaction path both flow concurrently at about the same linear velocity, thereby avoiding significant slippage of catalyst relative to hydrocarbon. A buildup of catalyst in the reactor leads to a dense bed and backmixing which in turn increases the residence time in the reactor for at least a portion of the charge hydrocarbon induces aftercraclcing. Avoiding a catalyst buildup in the reactor results in a very low catalyst inventory in the reactor, which in turn results in a high space velocity. Therefore, a space velocity of over or weight of hydrocarbon per hour per weight of catalyst inventory is highly desirable. The space velocity should not be below 35 and can be as high as 500. Due to the low catalyst inventory and low charge ratio of catalyst to hydrocarbon, the density of the material at the inlet of the reactor in the zone where the feed is charged can be only about 1 to less than 5 pounds per cubic foot, although these ranges are nonlimiting. An inlet density in the zone where the low molecular weight feed and catalyst is charged below 4 or 4.5 pounds per cubic foot is desirable since this density range is too low to encompass dense bed systems which induce backmixing. Although, conversion falls off with a decrease in inlet density to very low levels, we have found the extent of aftercracking to be more limiting feature than total conversion of fresh feed, even at an inlet density of less than 4 pounds per cubic foot. At the outlet of the reactor the density will be about half of the density at the inlet because the cracking operation produces about a fourfold increase in mols of hydrocarbon. The decrease in density through the reactor can-be a measure of conversion.

A wide variety of hydrocarbon oil charge stocks can be employed. A suitable charge is a gas oil boiling in the range of 430 to 1,100" F. As much as 5 to 20 percent of the fresh charge can boil above this range. Some residual oil can be charged. A to percent recyclerate can be employed. Generally, the recycle will comprise 650 F.+ oil from the product distillation zone which contains catalyst slurry. If there is no catalyst entrainment, recycle can be omitted.

EXAMPLE 1 A series of tests were conducted which illustrate the effect of reducing hydrocarbon partial pressure upon selectivity to debutanized gasoline and to C +liquid yield. The tests were conducted in an elongated reactor and the hydrocarbon partial pressure was reduced by addition of steam and nitrogen with the feed hydrocarbon. The ranges of conditions of the various tests were as follows:

Charge Stock Inspections The results of the tests are illustrated in FIG. 2 in which debutanized gasoline yield and total C +liquid yield, both reported as percent by volume of fresh feed, are plotted against total conversion at various partial pressures of hydrocarbon in the system and at various residence times. The pressure ranges given on the face of the graphs indicate the partial pressure in the system of all hydrocarbon vapors, cracked and uncracked, with the remainder of the reactor pressure accounted for by nitrogen and steam, both nitrogen and steam being used in all tests. For each partial pressure, conversion data is indicated for one or more residence times.

As shown in FIG. 2, at any given conversion level the selectivity to gasoline as well as to total C,+liquid increases with decreasing hydrocarbon partial pressure. Taking a 60 percent conversion level for purposes of example, when the hydrocarbon partial pressure is 16-20 p.s.i.g., the gasoline yield is 47.5 percent; when the hydrocarbon partial pressure is 10-14 p.s.i.g. the gasoline yield increases to almost 50 percent; and when the hydrocarbon partial pressure is 2-5 p.s.i.g. the gasoline yield increases still further to about 51.5 percent. Advantageously, a greater improvement in gasoline selectivity occurred in reducing hydrocarbon partial pressure from 16-20 p.s.i.g. to 10-14 p.s.i.g. than occurred in reducing EXAMPLE 2 Tests were conducted to illustrate the advantage of a crystalline zeolite aluminosilicate catalyst over an amorphous silica-alumina catalyst in a fluid catalytic cracking system. Both catalysts were tested under sufficiently low space velocity conditions that a dense phase bed formed in the reactor. The results are shown in table '1.

TABLE 1 Charge stock:

Characterization factor 12. 09 11. 95 Gravity, API 29. 7 29. 4 Sulfur, percent- 0. 42 0. 36 Viscosity, SUS at F.:

130 60. 3 g8 51.1 38. ii 37. 3 Carbon residue, ramsbottom, percent ASTM D-62 0. 23 0. 21 Aniline point, F 188 184 Bromine Number, D1150 2. 8 3.0 Pour point, D-97, F .10 Nitrogen, p,p.m 710 450 Metals, p.p.m.:

Vanadium 0. 2 0. 4 Nickel 0.2 0. 1 Distillation vac. (corres to 760 mm.Hg):

10% over at F" 568 656 30% over at F 659 622 50% over at F 744 699 70% over at F 845 809 over at F 979 939 over at F 901 Catalyst Kellogg activity (2-hour) 33. 8 50. 6 Operating conditions, reactor:

Fresh feed rate, b./d 13, 571 13, 704 Reactor bed temperature, F 926 935 Feed preheat temperature, F. 700 649 Reactor bed pressure, p.s,i.g 11.5 11. 0 Space velocity (total feed), wt./hr./wt. 3.94 3.07 Catalyst to oil ratio (total feed), wt./wt 12. 5 0. 8 Recycle, percent by volume of fresh feed. 74. 3 31. 4 Carbon on regenerated cat, percent by wt 0. 4 0.38 Conversion, percent by volume of fresh feed 75. 5 85. 5 Operation conditions, regenerator:

Regen. bed temperature, F 1,141 1, 166 Total regeri. air, M lb./hr 153. 7 166. 72 Lb. coke burned/lb. air, wt./wt 0. 087 0.083 Yields, percent by volume of fresh feed:

Debutanized gasoline 47. 5 61. 0 Butane-Butene 21. 2 21. 6 i-Butane. 7. 6 10. 3 n-B utane 2. 1 1. 7 Butencs 11. 6 J. 6 Propylene:

Propane 4. 2 5. 7 Propylene 8. 5 5. 9 Total licitlld recovery 105. 9 108. 7 C1 and l ghter gas, percent by wt 4. 4 2. 0 Coke, percent by wt 7. 73 7. 8 Inspections:

Motor, clear 81. 8 Motor, plus 3 cc. TEL. 86. 1 89. 4 Research, clear 94. 0 93. 4 Research, plus 3 cc. TEL 100. 4 98. 3

1 percent amorphous silica alumina. 2 60 percent zeollte, 40 percent sllica-alumina.

As shown in table 1, the zeollte catalyst system exhibited a conversion of 85.5 percent compared to only 75.5 percent for the amorphous catalyst. In addition, the zeolite catalyst system exhibited a 61.0 percent yield of gasoline compared to only 47.5 percent gasoline yield with the amorphous catalyst. However, while the total yield of C and C hydrocarbons is about the same for the zeolite and the amorphous catalyst, the proportion of these C and C hydrocarbons which are olefinic is lower when utilizing a zeolite catalyst in these tests. This is a disadvantage arising when utilizing a zeolite catalyst with extended residence times in a dense catalyst bed because C and C olefins are useful for the production of alkylate which can be blended with the gasoline produced directly by cracking to improve its octane value.

Example 3 Further tests were conducted to illustrate the use of the same type of zeolite catalyst employed in example 2 for fluid catalytic cracking not only at relatively high residence times involving space velocities low enough to permit a dense phase catalyst bed to form in the reactor but also at very low residence times within the range of this invention at which the velocity through the reactor is sufficiently high that no bed formation within the reactor and therefore no backmixing due to bed formation is permitted to occur. The results are shown in table'2.

Table 2 Test 1 2 3 4 Catalyst Catalyst bed tolmatlon Yes No Yes No Cracking temperature, F-.. 950 950 1, 000 1,000

Space velocity (total feed). 19.2 100 99.5% 100 Contact time, seconds 0. 5 2.0

Recycle, percent by volume 2. 4 5. 3

Conversion, percent by volume..- 72. 8 77. 1 76. 2 80. 9

Yields, peasant by volume of fresh fee 9. 9 10.4 11.7 11.3 6.6 6. 7 7. 5 9.0 14. 2 16.0 15. 8 l7. 7 6. 8 7. 6 8.0 7. 8 55. 8 60.2 56. 2 63. 8 4.8 4.8 5. 4.3 44. 2 47. 9 44. 8 50. 8 Total Ca-l-liquid 106.8 109. 107. 5 111.9

li ht r r nt 3.6 2.5 4.1 2.1 Coke, percent by Wt 5. 6 6.0 5. 0 4. 5

li ctane:

343531 clear 79.3 79. 6 80. 6 79. 3 Motor, plus 3%.. 85. 4 86. 2 86. 4 86. 3 Research, clear 92.3 92.6 93. 5 91.4 Research, plus 300 100. 2 99.6 99. 5 98. 7

1 Zeolite. 2 Bed baclnm'xing. 3 None.

A comparison of tests I and 2 of table 2, both conducted at 950 F., shows the deleterious effect of extended residence time when employing a zeolite catalyst. The residence time of test 2 was only 0.5 second and yet it exhibited a higher gasoline yield and a lower C and lighter yield than test 1 in which the residence time was considerably longer due to a lower space velocity and back-mixing arising in the dense catalyst bed. A comparison of tests 1 and 2 shows that an extended residence time gives arise to aftercracking which diminishes gasoline yield and increases the yield of products boiling lower than gasoline.

Comparing test 3 with test 1, both involving dense bed cracking, it is seen that raising the cracking temperature from 950 to l,000 F provided a significant increase in conversion but very little increase in debutanized gasoline yield and a higher yield of C, and lighter, showing that the high degree of aftercracking occurring in a dense bed reaction system prevents effective control of gasoline yield via temperature adjustment.

Comparing test 4 with test 2, both involving nonbed cracking and very low residence times within the range of this invention, it is seen that raising the cracking temperature from 950 to l,000 F. provided not only a significant increase in conversion but also an equally significant increase in gasoline yield coupled with a lower yield of both C, and lighter and coke, showing that the comparative absence of aftercracking at the very low residence times of this invention permits control of gasoline yield via temperature regulation. It is also noted that test 4 provided good yields of C olefin and C olefin which are valuable materials for preparation of alkylate gasoline.

Since table 2 indicates that in low residence time nondense bed systems gasoline yield can be effectively controlled via temperature regulation, it follows that a reduction in temperature might be useful on occasion in an operating plant to reduce gasoline yield as required by subsequent fractionator load or to decrease C olefin and C olefin production. However, no matter what the operating temperature is the gasoline yield at that temperature is increased by utilizing the control method of this invention.

A suitable reactor-regenerator system for performing this invention is described in reference to FIG. 3. The cracking occurs with a fluidized zeolitic catalyst in an elongated reactor tube 10, which is referred to as a riser. The riser has a'length to diameter ratio of above 20, or above 25. A full range hydrocarbon oil feed to be cracked is passed through pre heater 2 to heat it to about 600 F. and is then charged into the bottom of riser 10 through inlet line 14. Steam is introduced into oil inlet line 14 through line 18. Steam is also introduced independently to the bottom of riser 10 through line 22 to help carry upwardly into the riser regenerated catalyst which flows to the bottom of the riser through transfer line 26.

The oil charge to be cracked in the riser is a gas oil having a boiling range of about 430 to l,lOO F. The steam added to the riser can amount to about 10 weight percent based on the oil charge, but the amount of steam can vary widely. The catalyst employed is a fluidized zeolitic aluminosilicate and is added to the bottom of the riser. The riser temperature range is about 900 to 1,100 F. and is controlled by measuring the temperature of the product from the riser and then adjusting .the opening of valve 40 by means of temperature controller 42 which regulates the inflow of hot regenerated catalyst to the bottom of riser 10. The temperature of the regenerator catalyst is above the control temperature in the riser so that the incoming catalyst contributes heat to the cracking reaction. The riser pressure is between about 10 and 35 p.s.i.g. Between about 0 and 5 percent of the oil charge to the riser can be recycled. The residence time of both hydrocarbon and catalyst in the riser is very small and ranges from 0.5 to 5 seconds. The velocity throughout the riser is about 35 to 55 feet per second and is sufficiently high so that there is little or no slippage between the hydrocarbon and catalyst flowing through the riser. Therefore, no bed of catalyst is permitted to build up within the riser, whereby the density within the riser is very low. The density within the riser is a maximum of about 4 pounds per cubic foot at the bottom of the riser and decreases to about 2 pounds per cubic foot at the top of the riser. Since no dense bed of catalyst is permitted to build up within the riser the space velocity through the riser is unusually high and will have a range between or and 600 weight of hydrocarbon per hour per instantaneous weight of catalyst in the reactor. No significant catalyst build up within the reactor is permitted to occur and the instantaneous catalyst inventory within the riser is due to a flowing catalyst to oil weight ratio between about 4:1 and 15:1, the weight ratio corresponding to the feed ratio.

The hydrocarbon and catalyst exiting from the top of each riser is passed into a disengaging vessel 44. The top of the riser is capped at 46 so that discharge occurs through lateral slots 50 for proper dispersion. An instantaneous separation between hydrocarbon and catalyst occurs inthe disengaging vessel. The hydrocarbon which separates from the catalyst is primarily gasoline together with some heavier components and some lighter gaseous components. The hydrocarbon effluent passes through cyclone system 54 to separate catalyst fines contained therein and is discharged to a fractionator through line 56. The catalyst separated from hydrocarbon in disengager 44 immediately drops below the outlets of the riser so that there is no catalyst level in the disengager but only in a lower stripper section 58. Steam is introduced into catalyst stripper section 58 through sparger 60 to remove any entrained hydrocarbon in the catalyst.

Catalyst leaving stripper 58 passes through transfer line 62 to a regenerator 64. This catalyst contains carbon deposits which tend to lower its cracking activity and as much carbon as possible must be burned from the surface of the catalyst. This burning is accomplished by introduction to the regenerator through line 66 of approximately the stoichiometrically required amount of air for combustion of the carbon deposits. The catalyst from the stripper enters the bottom section of the regenerator in a radial and downward direction through transfer line 62. Flue gas leaving the dense catalyst bed in regenerator 64 flows through cyclones 72 wherein catalyst fines are separated from flue gas permitting the flue gas to leave the regenerator through line 74 and pass through a turbine 76 before leaving for a waste heat boiler wherein any carbon monoxide contained in the flue gas is burned to carbon dioxide to accomplish heat recovery. Turbine 76 compresses atmospheric air in air compressor 78 and this air is charged to the bottom of the regenerator through line 66.

The temperature throughout the dense catalyst bed in the regenerator is about 1,250 F. The temperature of the flue gas leaving the top of the catalyst bed in the regenerator can rise due to afterburning of carbon monoxide to carbon dioxide.

. Approximately a stoichiometric amount of oxygen is charged to the regenerator and the reason for this is to minimize afterburning of carbon monoxide to carbon dioxide above the catalyst bed to avoid injury to the equipment since at the temperature of the regenerator flue gas some afterburning does occur. In order to prevent excessively high temperatures in the regenerator flue gas due to afterburning, the temperature of the regenerator flue gas is controlled by measuring the temperature of the flue gas entering the cyclones and then venting some of the pressurized air otherwise destined to be charged to the bottom of the regenerator through vent line 80 in response to this measurement. The regenerator reduces the carbon content of the catalyst from 1:05 weight percent to 0.2 weight percent or less. If required, steam is available through line 82 for cooling the regenerator. Makeup catalyst is added to the bottom of the regenerator through line 84.

Hopper 86 is disposed at the bottom of the regenerator for receiving regenerated catalyst to be passed to the bottom of the reactor riser through transfer line 26.

We claim:

1. In a process for cracking a gas oil hydrocarbon feed to gasoline in the presence of a fluid zeolite cracking catalyst, the improvement comprising performing said process at a temperature between 900 and 1,l00 F. and a residence time of less than 5 seconds during which catalyst and hydrocarbon both flow concurrently through the process under conditions such as to avoid formation of a catalyst bed in the reaction flow stream, introducing to said process a diluent vapor which reduces the partial pressure of said hydrocarbon feed and produces a net increase in debutanized gasoline yield in said process, and recovering debutanized gasoline from said process in an amount including said net increase.

2. The process of claim 1 wherein the pressure is about 5 to 50 pounds per square inch gauge.

3. The process of claim 1 wherein the space velocity is at least about weight of hydrocarbon feed per hour per weight of catalyst.

4. -.The process of claim 1 wherein the linear velocity is between about 25 and 75 feet per second and the reactor length to diameter ratio is above about 20.

5. The process of claim 1 wherein the catalyst to oil weight ratio entering the process is between about 4:1 and about lSzl and the catalyst to oil weight ratio at any position along the flow path in the process is about the same as the entering ratio.

6. The process of claim I wherein the density of the material at the inlet of the process is no more than about 4 pounds per cubic foot.

7. The process of claim 1 wherein said diluent vapor is steam and is present in an amount between about 0.5 to 10 weight percent based on said hydrocarbon feed.

8. The process of claim 1 wherein said catalyst is charged to the process at a temperature of at least about 1 ,240 F.

9. The process of claim 1 wherein the diluent vapor is steam, nitrogen, methane or ethylene.

10. The process of claim 1 wherein the effluent stream discharges from the cracking reactor in a lateral direction.

mg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION November 2, 1971.

Patent No. 17,512 Dated Inventor) Millard C. Bryson and James R. Mur hy It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 7, line 3, before "feed" insert --low molecular weight-- Column 9, line 28, delete "99.3" and insert l9.3-

Signed and sealed this 22nd day of August 1972.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. Attesting Officer ROBERT GOT'ISOHALK Commissioner of Patents 

2. The process of claim 1 wherein the pressure is about 5 to 50 pounds per square inch gauge.
 3. The process of claim 1 wherein the space velocity is at least about 100 weight of hydrocarbon feed per hour per weight of catalyst.
 4. The process of claim 1 wherein the linear velocity is between about 25 and 75 feet per second and the reactor length to diameter ratio is above about
 20. 5. The process of claim 1 wherein the catalyst to oil weight ratio entering the process is between about 4:1 and about 15:1 and the catalyst to oil weight ratio at any position along the flow path in the process is about the same as the entering ratio.
 6. The process of claim 1 wherein the density of the material at the inlet of the process is no more than about 4 pounds per cubic foot.
 7. The process of claim 1 wherein said diluent vapor is steam and is present in an amount between about 0.5 to 10 weight percent based on said hydrocarbon feed.
 8. The process of claim 1 wherein said catalyst is charged to the process at a temperature of at least about 1,240* F.
 9. The process of claim 1 wherein the diluent vapor is steam, nitrogen, methane or ethylene.
 10. The process of claim 1 wherein the effluent stream discharges from the cracking reactor in a lateral direction. 